Manifestation of hydrogen bonding and exciton delocalization on the absorption and two-dimensional electronic spectra of chlorosomes

Vesna Eric, Xinmeng Li, Lolita Dsouza, Sean K. Frehan, Annemarie Huijser, Alfred R. Holzwarth, Francesco Buda, G.J. Agur Sevink, Huub J.M. de Groot, Thomas L.C. Jansen*

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

3 Citations (Scopus)
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Chlorosomes are supramolecular aggregates that contain thousands of bacteriochlorophyll molecules. They perform the most efficient ultrafast excitation energy transfer of all natural light-harvesting complexes. Their broad absorption band optimizes light capture. In this study, we identify the microscopic sources of the disorder causing the spectral width and reveal how it affects the excited state properties and the optical response of the system. We combine molecular dynamics, quantum chemical calculations, and response function calculations to achieve this goal. The predicted linear and two-dimensional electronic spectra are found to compare well with experimental data reproducing all key spectral features. Our analysis of the microscopic model reveals the interplay of static and dynamic disorder from the molecular perspective. We find that hydrogen bonding motifs are essential for a correct description of the spectral line shape. Furthermore, we find that exciton delocalization over tens to hundreds of molecules is consistent with the two-dimensional electronic spectra.
Original languageEnglish
Pages (from-to)1097-1109
Number of pages13
JournalThe Journal of physical chemistry B
Issue number5
Early online date25 Jan 2023
Publication statusPublished - 9 Feb 2023

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